Process for simultaneous cracking and polymerizing of hydrocarbons



June 17, 1941.4 SUBKW PROCESS FOR SIMULTANEOUS CRACKING AND POLYMERIZING HYDROCARBONS f origin'al Filed Aug. 12, 1955 2 sheets-sheet -,1

Liga! Gas Reacz'on A C/z amber frn ace Philip ubkow Feed 0u- *Y w j BYWy/ f f -ATT NKY..y

' P. sUBKw 1 .PROCESS FOR s IMULTANEOUS CRACKI-NG AND POLYMERIZ-ING OF HYDROCARBONS original Filed Aug. 12, 192,5 2 sheets-shet 2 Patented June 17, 1941 UNITED STATES PATENT OFFICE PRDCESS FOB SIMULTANEOUS ('IR'ACIKIN'G:y AND POLYMEBIZING F HYDRCARBONS Philip subkow, west Los Angeles, cani., signor y to Union Oil Company of California, Los Angeiles Calif., a corporation of California Gris-ina! application AugustV 12, 1935,I Serial No. 35,702. Dividedanol this application July 12, 193,8, Stiif. N0. zifgrg I (c1. iss-je) 2 Claims.

This invention relates to a process and apparatus for the formation of high anti-knock gasoline, and particularly to a process for the conversion of low anti-knock gasoline to high antiknock gasoline by a modification of the process^ A mers. Isomerization, although not strictly a polybranched chainhydrocarbons or alkylation reactions between aromatics and unsaturated low mo- `lecular weight hydrocarbons such as ethylene,l propane or butene, or straightV polymerization reactions wherein olefins such as monoor dioleflns are polymerized to higher molecular weightpolymerization'reaction in the sense that higher mo= "lecular weight bodies are formed, is included within this term since it occurs along with such polyv rnerlzation reactions. The term polymerization as here used is intended toembrace these types of reactions. for building higher molecular weight bodies by reaction of lower molecular weight hydrocarbons. The gasoline produced by this proc-n ess is termed polymer gasoline, and when prof duced as a mixture vwith reformed gasoline it is obtaining improved anti-knock qualities by molecular rearrangement, known as isomerization The conventional process for reforming gaso line consists in subjecting hydrocarbons in the gasoline range, preferably in vaporous'form, to high temperatures, under which conditions the gasoline is converted from one having low antilgnock properties to one having high anti-knock properties. The gasoline is then separated from the ilxed gases and normally gaseous hydrocarbons to form a stabilized and reformed gasoline.'

This process for the formation of high iso-octane number material is visualized as proceeding here termed reformed and polymer gasoline.

The ter'm "reforming is intended to embrace the reactionsof cracking or decomposition, dehydrogenation and isomerization by which low oc` tane material of gasoline or higher boiling range is covertedinto gasoline fractions of high antiknock properties. I A

The object of this invention is to reform gasoline under such conditions that along with the cracking, dehydrogenating, and isomerizing operations there is a parallel, subsequent, or conjoint through cracking, dehydrogenating and isomerizing reactions which yield as an intermediate or by-product, low molecularweight oleflnic fractions and chemical radicals with unsatisfiedv valences called residuals, In conventional re.

forming operations there islno attempt to control the subsequent `polymerization of these materials to retain and conserve those desirable antiknock characteristics and to polymerize the'gaseous residuals to liquid hydrocarbons of high antiknockvalue. The' process of this invention provides for controlled polymerization and conservation of these residuals and olens, particularly hydrocarbons those of the ethylenictype, in the reaction zones, thus favorlngcontinued decomposition of the'petroleum hydrocarbons and increased yield of high octane material over that resulting from a simple reforming operation.v A reformed gasoline containing increased percentages of polymergasoline of high octane value results.

The reactions here generically merization include alkylation lreactions wherein saturated hydrocarbons combine with unsaturated termed 1:1013v to yform high molecular *weight polymerizing reaction where the gases formed or: y

added t a reforming operation are converted into polymerized materials,'and a blend of reformed and polymer gasoline ls formed directly in the process. Broadly stated. the invention consists inr reforming liquid hydrocarbons, and particularly hydrocarbons in the gasoline range, to produce hydrocarbons having boiling points in the gasoline range and vapors containing hydrocarbons of *ve or less carbon atoms, which vapors are polymerized, separatelyif desiredybut preferablyin the presence of lthe gasoline, fractions produced by the reforming operation.`

The invention also contemplates the addition Aof hydrocarbons having've or less carbon atoms to the gasoline being polymerized to increase the ooncentration of these hydrocarbons.

Normally gaseous hydrocarbons such as. propane, butano, propylene or butylene may be polymerized. Instead of using the hydrocarbons having four or less carbon atoms. stabilized natural gasoline containing these fractions may be employed. it is preferred, however, to use hydrocarbons of the unsaturated type. Sources of such gases-are processes in which gas eiland/or fuel' oil arecracked at temperatures below 1000 that is, in the neighborhood of 850-950" F.

'I'he reforming operation, which is at least partially a combined cracking, dehydrogenating and isomerizing operation, may be aided by choice of conditions of temperature and pressure and of this nature are to be followed. Thus, 'the metals are best used when in finely,divided form. and better when supported on carriers. For example, the metal might Ibe formed Iby reducing the oxide of metal absorbed upon a carrier such as charcoal or silica gel in a stream of hydrogen. These methods are'well known and oonventional in the catalytic art.A The salts or acids are best formed' when precipitated on a carrier or fused with a carrier and ground into a une state. The clays such as bentonite and fullers earth are best used in their activated states, thus fuller's earth is used in the' acid'treated state.

` in which state their adsorptive activity is best Metals-Nickel,palladium, platinum, copper,

cobalt, iron, zinc, titanium, aluminum, tungsten, A

molybdenum, thorium;

Sulfides.-Cobalt,` iron, zinc,

nickel, manganese, tungsten;

Oxides-Alkali metals such as calcium, magnesium, barium, aluminum, chromium, zinc, manganese, silica;

Hydrozdes.-Chromium, alkali metal; Acids.-Molybdic, tungstic, chromic, phosphoric, arsenious, silica, boric;

SaZts.-Alum'inates, chromates, tungstates, va-

nadates, uranates, phosphates of the alkali earth metals such as calcium; and the phosphates, chromates and vanadates of aluminum, chromium or zinc; phosphates of molybdenum, tungsten;

ammonium'molybdate, aluminum sulfate; ladsorbents like fullers earth, bentonite;

Adsorbent charcoal or other adsorbent carbons;

Halides such as aluminum chloride, iron chloride, aluminum bromide and iron bromide.

When hydrocarbon fractions having a boiling range upto about 60G-650 F. are passed over these catalysts at temperatures from 662-1832" F. a reforming reaction occurs. In producing gasoline containing olefinic materials temperatures of about 8501050 yF. may be employed. Higher temperatures. in the neighborhood of 13801830 F. favor aromatic formation. The salts and oxides of the diflicultly reducible metals, as for instance, the alkali metals such as calcium, -magnesium, barium, require in general higher temperatures -for the formation of clens, i. e. temperatures in, the 'neighborhood of 1020-1380? F. The gases resulting may thenbe reacted in the presence of a polymerlzingcatalyst.

Catalysts which have been found to aid polymerization are termed fpolymerizing catalysts.

Such catalysts are fullers earthk absorbent carbon, phosphorous acids such as orthophosphorous acid, and phosphoric acid such as orthophosphoric acid. In solid form, aluminum oxide,

calcium oxide, carbonates of the alkaline'nietals,

` the oxides Yand carbonates of magnesium or beryllium, the acids of .boron and antimony, thoria,` 'zinc chloride or aluminum chloride, 'cadmium phosphate, aluminum sulfate in solid form, ad-

sorbent clays like bentonite, graphite, charcoal,

copper alkali metal salts (especially oxygencontaining salts), phosphates, borates, anti-v monates, boron trifluoride, either'alone or as a double compound with ethylene in theform of ethylene fiuoboric acid, cadmiumphosphate, and siliceous earths, tin, zinc, aluminum, chromium, silicon, lead or alloys of these metals.

In using the reforming and polymerizing catalysts, one skilled in the art willunderstand that the conventional methods of preparing catalysts broughtv out. Methods of increasing the adsorptive activity vof clays and adsorbent carbon are well known in the adsorption art. i K

`In using catalysts 'to be carried in the stream of gases, the catalyst, if it is boron fluoride, may

be fed as a gas to this streamer mixed'in the liquid state at low temperature. If the catalysts are solid they are best ground fine and carried in suspension by mixing with the liquid feed and carried along by the high velocity-ofthe vapors. The solid catalyst may also be positioned as a contact mass in the reaction zone and the vapors passed through the body of catalyst.

The reactions which have been termed polymerization reaction, and "reforming reaction" are parallel reactions. These reactions are generally reversible, the reaction in one direction being a polymerization reaction, and the reaction in the other. direction being .a reforming reac` tion. Consequently, in the polymerization operation and in the reforming operation, all reactions maypccur. In general, the polymerization reactions are favored by lower temperatures, while the reforming reactions are favored by higher temperatures, -the temperatures chosen should Ibe those at which the desired reaction predomlnates. The temperature will also vary and with the pressure.

with the feed stock, particularly upon its boilin! vrange and the chemical typeof the feed stock An additional factor is time. The polymerizationreactions and decomposition reactions may proceed further by allowing a longer'time of contact with the catalyst.

' Care must be taken to prevent the reforming reaction from going too far, thus forming light; undesirable fractions, or from allowing the polyf merization reaction to form undesirable heavy bodies by too long a polymerization contact time.

Various catalysts promote one or the other reactions favorably, under certain temperature conditions. The' temperatures and pressures herein disclosed are merely illustrative and are those at which the various reactions predominate, but the opposite reaction, whether it be reforming or polymerization, .also occurs. 'I'he temperatures are merely illustrative and are for feed stocks as herein described, and for pressures n that is, around S50-355 from atmospheric to 5000 lbs.

Thus, with metal catalysts, tin, zinc, copper, aluminum, chromium, silicon, lead. and nickel favor polymerization reactions in the tempera- Iture range between 350 and 700 F. Nickel fa'- vors the reaction in the lower of the said range,

F; These materials favor the reforming operation at higher temperatures. Iron and nickel vfavor the reforming operation above about 390` F. and in general, iron,

nickel', copper, cobalt, zinc, aluminum, chromium favor the reforming operation ranges above 932 F.

It will be seen that certain of the materials liat temperature the nature shown above, it is preferable thatv polymerization reactions be carried out'at lower temperatures here indicated, and the reforming operations at the higher temperatures, however, by applying higher pressures as hereinafter described. thev reaction temperatures are brought closer together and polymerization and reforming may occur together at the same temperature.

Catalytic oxidesk used for` these reactions, such as aluminum oxide either alone or combined with silica in the form of aluminum silicates, for instance, floridin or fullers earth, favor polymerization in the temperature range between 570 and '750 F. Preferably, aluminum oxide should be used in the neighborhood of from 640 to 700 F. Lime andr'other alkali earths or oxides or car-- bonates favor -polymerization in the range between 660 F. and 840 F. Magnesium and belryllium oxides favor polymerization reactions in the upper part of said range around 840 F. to 930 F. Aluminum 'chloride and boron triuoride are very active at .temperatures from 32 F. to 300 or 390 F.l Magnesium oxide, lime and silica, such as silica gel, can be used in reforming reactions in temperature ranges above 9301290 F. Aluminum oxide or aluminum sillcate such as fullers earth or fioridinor other forms will favor reforming above 750 F. Thus in using aluminum oxide, either alone vor in the form of. silicate, the temperature ranges should be adjusted depending on the form of the reaction which is to be favored. In operating in the upper ranges around '750 F. aluminum oxide will have a favorable influence on both reactions, aiding inthe decomposition in the higher molecular weight liquid hydrocarbons, and aiding in the lower molecular weight gaseous hydrocarbons. The temperature range should be chosen to form a balance between the two.

Of the salts. or adsorbents which accelerate polymerization reaction, the alkali metal carbonates, phosphates and borates are active in the neighborhood of 'Z50-930 F.; bentonite is active from G60-840 F.; phosphoric acid is active from 35o-475 F. Absorbent charcoals and carbons favor the polymerization' reaction at around '150 F. Above these temperatures, and

particularly at substantially higher temperatures reforming'is favored by these catalysts. Calcium aluminate, ammonium molybdate favor the reforming operations at temperatures of 930-1290 F. and higher. Aluminum sulfate and phosphoric acid are active in reforming reactions above 660 F. and very active labove 930 F.'

Mixed catalysts composed of mixtures of any one or more of the above reforming catalysts, and any one or more of the above polymerizing catalysts, which are active, i. e. promote and'accelerate the reforming and polymerizing operation in the neighborhood of 70D-930* F. will permit of the joint and favorable reactions of reforming and polymerization when operated at temperatures between about '10D-930 F. at pressure`s of about 'l5-1500 lbs.

Higher pressures favor-,the polymerization reaction and therefore, by .thev amplilcation of pressure, the tolerable temperature for polymerization is increased. At the same time pressure tends to decrease the reforming operation. and thel two operations may be broughtcloser tngether by the application of pressure. By choosing a'temperature intermediate the preferred' reforming and polymerization -reaction tem'perature at atmospheric pressure, and applying high pressure 'in the neighborhoody of 1000-5000 lbs.

the same catalyst may be used for both reactions.

It may -be chosen to use a catalyst or catalyst l mixtures whose temperature at which they ac` celerate the reforming operation, and the temprature at which they accelerate the polymerization operation, do not lie far apart. Thus, for

instance. one may choose catalysts which are active, i. e. promote or accelerate, in reforming at temperatures in the neighborhood of S40-1060* F., and choose catalysts which are active in, i. e. promote or accelerate, the polymerizing reaction at temperatures ranging from about 570,-840 F. at pressures ranging as low as atmospheric.

The liquid gases may be washed with alkali to free them of hydrogen sulfide and they can then be charged. The charging stocks to the reforming operation may contain organic sulfur bodies which will poison the catalyst. One may either remove these bodies or use a catalyst which will not be poisoned in these bodies.

The following of the above referred to catalysts are noteasily poisoned by the sulfur and sulfur bodies present in the charging stocks here used. Metals: colbalt,. iron, zinc; sulildes of cobalt, iron, zinc,- niekel, manganese, tungsten; oxides of chromium, zinc, manganese, aluminum; chronium hydroxide; molybdic. tungstic, chromic,

phosphoric, arsenious, silicio, boric acids; phosesl phates of alkali'metals, molybdenum, tuiigsirxfi'- ammonium molybdate, aluminum silicate, fullers earth. e f

Water and oxygen and traces of alkali poison aluminum oxide and fullers earth catalysts.- Small percentages of moisture in suchAcatalysts as hereinafter described may be tolerated. Oxygen also poisons aluminum oxide, fullers earth, and the metal catalysts. Air should be excluded.

' A good catalyst for the polymerization reaction is aluminum oxide preferably in the form of fullers earth or, artificial fullers earth formed by co-precipitating silica and yaluminum oxide from a mixture of sodium silicate and aluminum sulfate. The aluminum silicate is washed neutral and dehydrated. It is preferred that the f for instance, isopropyl chloride may be introduced to aid the polymerization reaction. Apparently, the isopropyl chloride is decomposed in the reaction/zone and forms free hydrochloric acid.

vIt'has been found that the alkyl chlorides are conveniently formed by passing a mixture of unsaturated hydrocarbons such as butylene and propylene over the above Vfullers earth type catalysts as previously disclosed at ordinary temper.

atures from about 20D-400 F. the alkyl chloride may be introduced either in vapor form as produced by the chlorinatlng reaction, or first condensed, and then introduced in liquid form. The

amount of alkyl chloride required varies from.

4one-tenth to one percent, preferably to about `this step practically difcult.

one-half percent of the reaction vapors.

'I'he catalysts here employed may be used in the reforming or polymerizing processes either as a catalyst body or as a mixture with incoming feed. In usingthe catalyst as a catalyst body, the reaction zone in the tube or chamber is charged with the solid catalyst and the reaction vapors'are passed through the body .of the catalyst. It is possible, however, to use thev catalyst as a slurry with the incoming feed, in which case the reaction zones are empty except for the re,

action mixture. When the vaporized hydrocarbons carrying the catalyst ground lline in suspension pass through the reaction zone, the high velocity of the vapors and the fine particle size of the catalyst prevent sedimentation of the catalyst in the tubes or chambers.

tures for the reforming reaction than would be possible without the catalyst. y 1

While the -processes of reforming and polymer-l ization are two distinct processes which may be separated-'the one fromnfthe other by careful choice of conditions and catalysts by control of conditions, as previously described.y the A two processes may be interwoven. r

In operating a combination of reforming and, polymerization such as, for example, lthoseshown. in .Figures 1, 2, 3 and 5, where saturated normally,

gaseous hydrocarbons are introduced intopthe reforming zone, this reforming maybe operated at a relatively .high temperature to formlarger amounts of unsaturated normally gaseous hydrocarbons in the lvapor mixture passing to the polymerization stage. In suchaproc'ess an active y dehydrogenating `or reformin'g catalyst'may be In carrying out the process of this invention:-

` 4 the following principles may actas a guide. The

feed of liquid fractions is one preferably having an end point not in excess of 650 F. Usually a heavy gasoline fraction boiling between BOO-500 1' F. will prove satisfactory. 'The reforming, cracking or dehydrogenation is best carried out at a temperature plane higher than that at which the polymerization reaction is carried out. It is desira-ble also to control these reactions so that they do not proceed to the ultimate stage oi!` carbon,`hydrogen and methane formation or to Y the production of high boiling fractions in the fuel oil range. It therefore will be desirable in one form of this invention to use relatively high temperatures and short times of contact in the reforming` zone. and to cool the ,reaction products produced by ther dehydrogenating and'cracking reactions before passing them to the polymerization reaction zone. The yield -of polymerization products may be increased by adding to the reaction mixture from an extraneous source hydrocarbon-materials of five or less carbon atoms.' The polymerizing vreaction including addition of unsaturates to unsaturates and alkylation in.

poly-molecular reaction is favorably influenced by increasing .the concentration of the reactants. 'Ihis may be accomplished by increasing the pressure, and also by adding materials undergoing me'rization and-reforming operations, as herein described. 'I'he saturated normally gaseous hydrocarbons undergo dehydrogenation and polymerization during the reforming operation. The decomposing reactions occur best at low pressures, the polymerization at higher pressures. It

therefore may =be desirable to increase the pres- -sure in passing through the polymerization stage;

The difficulty of compressing hot vapors makes It is, therefore, desirable to compress only -the cold feed and to operate the whole system under the desired high `pressure for the polymerizing reaction. -The use i of catalysts permits the use of lower pressures for the polymerizing reaction and lower temperaemployed. The temperatures to beemployed may be inthe upper portion of the rangesuggested for the reforming catalyst.,` Another procedure to be followed in this connection is to carry the: n, reforming on at relatively, high temperatures to f produce large amounts of gas by extensive cracking of the feed stock. Thus, for instance, in operating on a charging stock composed of crude gasoline of from 45o-500 F; end point. the craclr-` i ing may be carriedon to produce large gas yields rin excessof 40G-501i cu. ft. per barrel of charging stock. These gases, together with any added gas I may be passed to the polymerization stage. In this connection the gasoline fractions may be first removed and the lighter gases polymerized or the polymerization `may be carried on in the presence of the reformed gasoline fractions.

The cracking and dehydrogenating processes of reforming are reversible reactions, and Iconcomitant with them occur polymeizing'and hydrogenating reactions. yThe unsaturated bodies formed as a result of the cracking and dehydrogenation are extremelysactive and tend to com bine with each other.k The light unsaturated gases tend to polymerize with themselves and with the unsaturatedhigher molecular weight bodies present in the reaction zone. It is therefore possible to combine the reforming and `polymerizing processes. and to carry o`n the polymerization lof vthe lighter fractions 4(five carbon, and 'particualarly four carbon and lower) in the presence of the hydrocarbons within the gasoline range formed as a result of the reforming operation. By

such a combined process, the low molecular weight oleflnic products of the reforming processes are continuously and progressively removed by polymerization from the reaction zone as they are formed, thus favoring continued reforming of the petroleum hydrocarbons and an Iincreased yield of high octane material over. that resulting from a simple reforming operation. The lower molecular weight unsaturated hydrocarbons, particularly those of iivecarbon atoms and less are polymerized with themselves` and are also polymerized by addition `of the higher v'molecular weight liquid hydrocarbons of six' carbon atoms and more formed in the reforming reaction, or present in the hydrocarbon material lforming the charge to the operation. A

If desired, instead of -us'inga mixture of cataf lysts, the catalytic zones may beseparated and thereaetion mixture passed separately or alternately over ar dehydrogenation andipolymerizae tior catalyst. This may be accomplished by pass-A ing the mixtureV through a series of tubes of the'.

,nature of cracking rtubes .connected togetherby return bendsand the tubes filled alternately withr in a number of runs so that the mixture is ret -formed and polymerized in repeated passages i firstr heated to the reforming temperature in the reforming tubes, then cooled to a lower polymerizing temperature in the polymerization zone. If desired, temperature alone may be used to j produce the desired reforming and polymeriza- 1 tion without using catalysts in the tubes.

While catalytic operations are preferred, certain of the advantages of this operation are prev served in non-catalytic processes thus either thel reforming or polymerizing reaction or both may It is a further object of this invention to subject gasolineand kerosene and heavier petroleum fractionsr in the presence of a normally gaseous hydrocarbon to a reforming and polymerization reaction, preferably in the presence of catalysts which will accelerate and aid the reforming and be operated without the aid of catalysts to obtain a great number of the advantages of the operation. f

'Another arrangement which may be used is to carry out the process in a heated chamber through which are passed cooling tubes. Crackpolymerization reactions.

It is a further object of this invention to subject gasoline and kerosene and heavier petroleum fractions to a reforming operation and then to subject the product of the reforming operation to a polymerizing reaction, preferably in the presenceof a polymerization catalyst.

It is a further object of this invention to subject gasoline and kerosene and heavier petroleum fractions to` a. reforming operation, and then to subject the product of the reforming-operation in the presence of added normally gaseous hydrocarbons to a polymerization reaction, preferably in the presence of a polymerization catalyst.

It is a further object of this invention to subject'gasoline and kerosene and heavier petroleum fractions to a reforming and polymerization reaction in the presence of a reforming and polying'and dehydrogenating catalysts may bek de- "posited on the' warm walls of the chamber,l and in order toy remove undesirable gum-forming constituents such as dioleiine. Olefins other than those that react readily with free oxygen are not dljectionable constituents in gasoline,

I and.their'""conservation is desirable. Retention of these desirable unsaturated compounds may be accomplished by a controlled polymerizing action which only affects those unsaturates which 'are most readily polymerized and leaves the othmerization catalystunder such high pressure conditions and such conditions of temperature that the vpolymerization and reforming operations are both aided by the presence of the polymerization and reforming catalysts.

It is a further iobject of this invention to subject gasoline and kerosene and heavier petroleum fractions to a reforming operation and subsequently to a polymerization operation under such conditions of temperature and pressure that the reforming operation is carried out at a higher temperature than` the polymerization operation wherein the reformed gasoline composed of gasoline and kerosene fractions, and containing norers to contribute their high' anti-detonating characteristics of the fuel.

The process of polymerization and also of reforming results in a product' which is composed of a polymer and reformed gasolinefraction of high octane and having an end point of. from 3D0-400 F. depending on operations, a heavy gasoline-kerosene fraction. having an end point of about.500550 F. and av heavy portion.` The sene" is recycled. While the figures describe the .total return; it /willbe understood that only a portion may berreturned and/the remaining portion lsent tostorage or re-run'on blending stock with the polymer and reformed gasoline.

It is therefore an object of this invention to subject kerosene and gasoline and heavier petroleum fractions to a reforming opration in the 'V1 presence of a reforming catalyst.

1t is a. further -object of this invention to form 'fareformedand polymer gasoline by subjecting gasoline, kerosene and heavier'hydrocarbons, to a ltion. of the lighter hydrocarbon fractions, and

particularly, those which are normally .gaseous in the reforming operation.

heavier fractions called heavy gasoline-kero- 4 mally gaseous hydrocarbons are ,subjected to a lower temperature for polymerization of the polymerizable hydrocarbons at that temperature and pressure.

This invention will be better understood by y Figure 5 shows a design and flow sheet of a Y* combined polymerization and reforming operation, and a furnace structure for the control of A temperature in the various coils of thefurnace;

Figure 6 shows a-simultaneous polymerization and reforming operation wherein the polymeri zation and reforming operations are carried on separately, and the products are combined and treated together.

Figurefl represents a schematic ow sheet of a combined reforming and polymerization process in which the reforming is primarily conducted in one zone at relatively higher temperature and polymerization in another zone of relatively lower temperature. In Figure `1 gasoline, kerosene, or gas oil fractions having endpoints under GOO-650 F; to be reformedeare fed through line `I by pump 2 through valve :landline I into the reforming the polymerization y coil 'I in furnace 8. 'I'he reforming catalyst may be added before passage to the heating coil through line 5 controlled by valve 6. The mechanism for the addition of the solid catalyst to the oil stream is shown schematically as indicated. Mechanisms for the addition of solid material to liquid being well known in the chemical engineering art. The reforming catalyst may be one of the previously mentioned catalystsor may be a mixture of reforming and polymerization catalysts. The temperature of the reforming operation will be chosen to correspond with the catalyst used in accordance with the principles herein-y above discussed.

'Ihe reformingstream containing the catalysts may be treated in one of two ways. If the prior reformlngoperation was made in the presence of a catalyst or catalyst mixture different from those which it is desired to have present in ythe polymerization zone, the stream is by-passed by closing valve I4 and opening valves I0 and I6. 'Ihe stream of catalyst and oil vapor is then passed through line 9 and meets. oil residuum such as fuel oil entering at I I to act as a dousing medium to wash out entrained catalysts and separate the vapors from the dousing medium in the separator I2. The temperature maintained in the separator is about 500 F., to insure the vaporization ofthe gasoline. fractions. The mixture of oil and catalyst is removed through valve controlled line I3and the vapors of gasoline and lighter fractions including the hydrocarbons of four and less rcarbon atoms, pass through line I5 and valve I into line 9'. Howevenif it is desired that the catalyst present in the reforming coil 'I and catalysts entrained in the` vapors passing therethrough be also present in the polymerization zone, valves I and I6 remain closed and valve I4 is open. In`l the -event the operation in chamber I2 is carried out, additional catalysts may be ,added through line I1 or provided as `catalytic mass in the reactor chamber 29. It may be foundv desirable to add fresh catalysts to the reaction mixture. Also, in the event that vthe operation in chamber I2 is not carried out, the reaction mixture passes through line 9' in order to increase the concentration of active catalysts in the `,reaction mixture.

The reforming operation may be carried out with the` omission of catalyst introduction through 5, and-the entire reformedmixture may be passed either. through I4 or by-passd to I2 andthe separated gasoline sent to 'reactor chamber 29 in the same manner as previously de-. scribed. The-catalyst added through I'I'is preferably chosen from among`the polymerization catalysts herein previously disclosed. In order to increase 'the concentration of light hydrocarbons'there lmay be added, through line I8,

liquid gases produced, in the stabilizer 46 asv will be hereinafter described. There may be also added at thisv point liquid gases from an extraneous source #through line 2l and pump 22.`

'Ihese gases are preferably propenes, butenes, ethylene, or mixtures 'of these hydrocarbons with the saturated hydrocarbons of` four or less car'- bon atoms. The mixture" is formed inline 9'. In the event that the cooling operation in chamber I2 and the cooling effected by the addition of the-liquid material through lineV I8 and vaporization of this material has reduced the temperature below the chosen reaction temperature, the mixture may be by-passed through line 23 and reheating coil 25'in furnace B'by the proper manipheater will then adjust the temperature in line 28 to the proper reaction temperature to be maintained in reactor 29. In the Vevent that the reactor does not contain the'mass catalysts in theA '5 form of a contact mass in the chamber, it becomes merely a reaction chamber to give reaction time to the mixture. In operating the reactor without the catalyst mass it would be advisable to direct the ilow of vapors and entrained l0 catalyst downwardly by adjusting the valves 28a in lines 28 and valved line 29 and valves 3Ia and 32a in line 3I so that the ilow will be downward through the reactor and into fractionator 33. If the catalyst contact mass is used, 'it may be del sirable to flow the vapors upwardly through the reactor and in which Acase by proper manipulation of the valves 29a, 28a, 3Ia and 32a, the flow may be properly directed. Gasoline thus formed will result from thereforming reactions operating on the charge to coils I and on polymerization of the reformed `vapors and gases.

` The reformed and polymer gasoline then passes through a fractionator 33 containingl the usual,

reux cooler 42 which may be either internal orl external. `The heavyr fraction, containing the recycling to the reforming operation via line I9 or is removed from the system partially or totally. 'Ihe reformed and polymengasoline is removed throughlde stream take-ofi 38` into tank 39,

' passed by pump 40 4throughheater 4I and line 45 into thestabilizer 46. Uncondensedgas from the iractionator passes through line 43, compressor `43a and line 44 into the stabilizer 46. The gasolines and gas are separated into `a stabilized gasoline removed through line 5I, valve 52, and cooler 53 and the liquid gas fraction containing butanes,

butylenes,propanes, propylenes, some ethane' and ethylenes in liquid form pass into tank 56 and circulate by pump 5'I through line 20 as previously described. Heat is supplied to the bottom of the tower by circulation from a lower tray through line 41, heater 49, and returned through Y line 50. The uncondensed and fixed gases are removed through line 54, controlled by valve 55.

The conditions to be maintained in heater 1 and in'the reactor 29 are those previously described and must be adjusted lfor the stock and catalyst employed as will be well understood in the art, f

In carrying out the process shown in Figure 1,

any one of the catalystshere described may. be employed, but the iiow will -be explained using one of the catalysts merely to illustrate the prin-` ciple of carrying out the reaction.

It will be understood that the other catalysts may be used with the proper control of' temperature and pressure-according to the principles hereinabove fully described.

A kerosene fraction .having an end point of about 550 F. is passed through une: and is intimately incorporated to form a slurry with molybdic acid, molybdenum sulde, or calcium aluminate, and ,is heated to a temperature of about 930 t0'1290 Fain coll 1. The mixture iS then passed through line 9 into chamber I2 in \which the catalyst and the oil are withdrawn and the vapors at a temperature of about 450 F. are withdrawn through line I5. Material is added through line I8 and the mixture at a temperature ulation of valves 9a, 24 and 21a. This control 75 of about 350 to 400 F. is introduced intochamagarrarse bei ze which is charged with a phosphoric acid catalyst in the form of orthophosphoric acid deposited upon a fullers earth base. The pressure maintained in the coil 1 and the chamber y29 is about 500 to 1000 lbs.

Figure 2 shows an operation of reforming and polymerization wherein the reactions occur in the pressure of an activating` material'which acts as apromoter 4to the reaction, or inthe presence of 'an' extraneous material which aids in producing improved characteristics in the nal product. As

previously described thefcatalysts may be either added to the material entering the reforming operation or present in the reformingtubes or may be placed in the polymerization reactor. If the gas stream contains catalysts, it passes together with the catalysts through the polymerization reactor. It has' been found that on using polymerization and reforming catalysts of the adsorbent clay type, such as fullers earth. or on chloric acid gas or alkyl chlorides which reactat the temperature reaction in the presence of these catalysts activ-ate these catalysts. It Vhas been found additionally, that these alkyl chlorides are themselves quite readily polymerized into higher polymerization kin 1 maybe digested to aid polymerization in chamber 2'9 free of catalyst.

In carrying out the processshown in Figure 2 the feed is described as being madeup of gasoline `fractions to which may be added the alkyl chlorides. It is of course possible that the feed may be composed of alkyl chlorides alone. However, it is preferred to operate the. process in Figure 2 whereby the alkyl chlorides are added to the gasoline and in the event the alkyl chlorides areA used as a promoter in the catalytic using base catalysts likealuminum oxide; hydropolymerization reaction they will be added to v the reaction mixture entering the polymerization zone. Heavy gasoline orkerosene passes through line I, pump 2, to be passed with stock a'dded through valve 3 and pass then into line 4 and valve 3 into reforming coils 1 in furnace 8. Alkyl halides may be fed through `line 60 and valvev 60a into reaction coil 1, or in the event that the feed is composed entirely of these halides; material is not 'introduced in line I. If it is desired instead of feeding halides through line 60, valve 60a may be closed and the halides may be introduced into line 9. Polymerization catalysts is introduced into the stream passed into line 4 as previously described by any well known solid feeding mechanism. The pointof introduction should be prior to the introduction of the stream into coil 1 unless the catalyst is contained inside the coils. Reformed material passes through line 9. 4Before entering line 9 it meets liquid gas introduced through line i8. These liquid gases may be introduced from stabilizer 46 afs later described or may come from an extraneous source.-

or may be both. The reactor 29 may be either as an additional Contact catalytic zone m -which case the catalyst ismaintained in the reactor as a contact mass or the reactor may be -empty and merely provide 'reaction time.

The material passes through line 9 controlled by valve 9a and through thev reactor 29, passes through 75 '7 une :2 and valve :2a tc fractionatcr n. rn the event-that the reaction is completed in .coils 1, the reactor'may be by-passed by closingvalves 9a and 32a and the vapors passed through line 3|. controlled by valve Ila directly into fractionator 33. In fractionator material is sepa'- rated into a heavy residual fraction and is with- The bottoms areY re drawn through line 34. heated by circulation through linesY 23, pump 23a, heater 26 and line 21. Incompletely converted gasoline is withdrawn through line 36 and pump 31 to act as recycle stock iis-previously described. The reformed and polymer gasoline is withdrawn throughline 38 into tank 29 and passed through pump 40 and heater 4I stabilizer 46. 'I'he gases uncondensedby cooler 42 pass through line .43, "compressor 43a into stabilizer 46. In stabilizer 46 the gasoline and gases are .separated into a stabilized, reformed and polymerized gasoline which is withdrawn through line 5I and cooler 53. Bottoms are circulated through line 41, heater 49 and line 60 to provide heat in the base of the column. Leiquid fractions composed of butane, butylene,^propane, propylene,v ethane and ethylene are withdrawn fin liquid form into tank 66 and passed to line vcontrolled by valve 6Ia to the reaction chamber 62 for conversion into the halide.n

It has been found that unsaturated hydro! carbons in the nature of propylene, butylene, amylene will react with hydrochloric. acid in the presence .of activated fullers earth or aluminum .oxide at. temperatures from 32390 Fito form alkyl halide. Propylene will add in thepresence `of hydrochloric acid at temperatures from 32-390"J F. to hydrochloric acid -veryxsmoothly` l The alkyl chloride thus formed may be introduced into the reaction stream by passing through line 63, valve 64 and line t5.l In passing through 6,5 it passes as a vapor and may be introduced into line' 9 to activate the polymerization in reactor 29. It. has been found that as much as from one-tenth to five-tenths percent of isop ropyl chloride when added to the gases enter- `ing the polymerizer reactor chamber 2-9 4accelerates polymerization reaction markedly. The chloride may be passed via line 60 and valve 60a into coils. 1. Instead of passing the isopropyl chloride'as a gas the isopropyl may be condensed by passing through line 63a, valve 64 remainingv closed to ycooler 66, collector 61 and unconiensed gases may be'removed. through valvedline 68';

the condensate -is fed byI pump 69 through valved line 10 as previously described. `The hydrochloric acid may be added into the stream entering the reactor 62 throughline 1I. In operating in the presence. of isopropyl chloride, it would be advisable to insure that the gases and liquid are moisture free. Provision will have to be made for separting free hydrochloric acid froml the vapors in 54 and from the various condensates l methane,

fullers earth or aluminum oxide as previously de" scribed. The temperature maintained in reactor 62 is as described, under. 390 F. Dry hydrochloric acid gas is f ed through 1I and alkyl chlominum oxide and oil. The temperature maintained in coil 1 is in the neighborhood of 930-1020 '.F. and the temperature inreactor 29 is from G40-730 F. This temperature is maintained by the introduction of material through 20 orthrough cooling the gases entering through ride is introduced into line I8 the material entering line 4 is a slurry of the fuller's earth as alu- 9 by an interchanger, as will be understood although not shown in the drawings, or by the control inthe reactor 29 as shown in Figure 3. Cooling in line 9 may be provided as shown in Figures 3, 4 and 6. Pressure maintained in coil 1 and reactor 29 is in the neighborhood of 50G-1500 Figure 3 shows schematically a combined process of reforming and polymerization process in which. separate .reforming and polymerization zones are provided. A reforming zone is provided in coil 1 in which coil `polymerization may also be effected if desired. Provision is made for the control of the temperature in the polymerization zone 29. The polymerization, being exothermic, the-temperature in the reaction chamber 29 tends to rise, and itis desirable to control the temperature to prevent excessive'increases in temperature.

Feed oil is introduced under pressure through line I and may pass either through line 'Ia and valve 2a or' through line Ib and valve Ic, or through both to the reforming coils 1. It is preferred, inthe event that the feed is a mixed feed' containing a, wide range of boiling fractions such as gasoline, kerosene and gas-oil, to rectify the feed by introducing it 'through line Ib and valve 'Ic into the fractionating chamber 33. In this chamber it meets the hot vapors from the reac-- tion zones and aids in the fractionation of these lvapors to form a heavy residual fraction 28 composed of the heavy ends of the charging stock and the heavy ends of the polymerized and reformed gasoline. boiling fractions is removed through line I9biand circulated through line I9 to meet anyv portion of material by-passed through line Ia if any such" is by-passed. If desired, a portion of the liquid gases which are to be polymerized are introduced through line 80 and the mixture is then .passed through line I a, heat exchange coil 3a, line 4 into the reforming coils 1 positioned in furnace 8. At

the outlet of coil 1 the reformed gasoline is doused.

A side cut of intermediatel 2,245,735'. withdrawn from the system by treatment with' the polymerization reaction in chamber I2. With some catalysts where steam is either an aid or is not a detriment to the polymerization reaction, steam may be used at thisv point. A spray of wash oil I2a is passed over the mist extraction and fractionating elements I2b to insure separation of entrained materials and heavy ends of the vapors. Instead of passing the vapors -through this chamber, the chamber may be -by-passed by proper control of valve I 0 in line 9 and valve 9a in line 9 tov pass the vapors around the separator. 'I'he vaprs are then passed to the polymerizing zone 29. Instead of' passing the gases through the reforming zone, or in addition -to passingthe gases through the reforming zone, they may be; added to the vapor in line 9' through by-pass line I8 by proper control of valve I8a and valve 80a. 'I'he mixed gases and vapors are then passed through linel 9' into the reaction zone 29. f

In order to control the temperature in the reaction zone 29, the liduid gases may be expanded through spray 8| by proper control of valves 82 and also by circulation of cooling fluid through the cooler 83 'via lines 83a and 83h. Inv operating the separator I2 in such manner that only the light fractions of y gasoline are separated, the temperature of the outlet vapors may sometimes be vbelow the desired temperature in the vpolymerization chamber 29.A Thus, kfor instance,

the vapors issuing through line I5 may be inthe neighborhood of 40G-450? F. while the reaction zone may be of` atemperature of 600 F. and' above. `Under those circumstances it'may be desirable to heat the reaction chamber 29 instead of cooling it. To do this the cooler 83 may be converted to a heater by circulating a heating fluid through the coils of the cooler 93. 'This cooler may be of the closed tube sheet type, the cooling fluidI circulating out of contact of material in the reaction chamber 29. The gases enterby contact with relatively cold heavy oil such asv fuel oil entering through line II and the partially cooled gases are Mthen `passed through heat. exchanger 3b fromwhich point they may be passed directly to the polymerizing chamber 29 via line 9', o r rst passed through the separator I2. In

separator I2 the heavy ends are removed through 1 line I3 and the vapors withdrawn from line I 5.`

*.The stripping of the bottoms to insure the removal of the gasoline fractions is aided by the introduction of fixed gases such as hydrogen, carbon dioxide or liquid-gases used in ing through valves 82 and spray 8l may be heated by passing through valves 84 and 86 and heater 85 by the proper manipulation of valve 81'. Any desired proportion of the gases tobe added for polymerization may be added in this way. Such gases thus added yare not subject to the reactions occurring in the reforming coils 1. .If it is desired to polymerize these gases without subjecting them to the reforming operation all'the gases maybe introduced in this manner.

The heavy polymers formed in the reaction zone and which are riot volatile at the temperature in chamber 29 are withdrawn through 34a and the vapors are withdrawn through line 34 to be passed to fractionator 33. There they pass countercurrent to the feed Ib and the reflux formed by cooling coils 42. In addition -to the heavy cut I9b, a reformed and polymer gasoline is withdrawn through the side cut into tank 395" and passed by pump 49 through heater 4I into" the stabilizer 46. The uncondensed vaporsI pass through line 43, compressor 43a into the stabilizer 46. In the stabilizer, the gasoline is separated intol a stabilized gasoline, withdrawn through 5I and cooler 53. 'I'he bottoms are rehoile'd by circulation through line 41, heater 49 and ref turn line 50. A liquid light hydrocarbon'fr'action withuiawn through une ssa into chamber sei-and additional gases through valve 81 coming from storage 89. These liquid gases are similar to those in 20 and are derived from other refinery sources. These gases may be sent through line 88' or 80 as previously described. f

In operating the process according to this flow sheet the temperature in coil 1 may be from temperature then employed may be from The reaction shown in Figure 2 may also loe carried out in Figure 3 in which case the reforming catalysts may be fed as a slurry in line t," separated in chamber l2, and the polymerization catalyst bedisposed as a contact vcatalyst mass in chamber 29. The temperatures and pressures `discussed with relation to Figure 2 may be applied to the process of Figure 3. A

' The catalysts tobe used in the reforming operation may be either introduced into line ia by a feeder as previously described or may be positioned in the coils of reforming coils 1. The reaction chamber 29 maybe charged with contact mass catalysts or the 'catalysts may bein- 'troduced intoline 0' to pass with the vapors through line 9'. It is preferred, howevenin the structure shown-in Figure 3, to charge reaction chamberl29 with catalysts.

In the operation according to the flow sheet shown in Figure 4, the polymerization and the reforming operation are carried out in'one zone. The feed which consists` of kerosene and gasoline fractions containing added thereto propane, butane, propane.` butene, ethane, and ethylene produced as previously described, is passed under pressure together with the catalyst, if an en- 56a contains the hydrocarbons ranging from butanes and butylenes, propane and propylenes to ethane and ethylene. These are recirculated through line to be sent to reformer coils 1.

The temperature chosen in Figure 4 in operating with fullers jearth may be in the neighborhood of 8401020 F.; the pressure inthe neighborhood of 500-5000 lbs. The other conditions willjfollow those described with regard to Figure 3. i

I In view of. the fact that the polymerization reaction using certain catalysts 'as previouslydescribed, operates best at temperatures lower than the' reforming operation, the formr of heaterk shown in Figure 5 provides for reaction zones of y alternately' high and low temperatures in which' the reaction mass is rst passed through high temperature and then l'ow temperature zones.

The reforming catalysts may be positioned in the high temperature zone and polymerizing catalysts in the low temperature zone or the mixed catalysts may be used in both zones. The furnace 8 is divided by vertical partition walls 00 to form chambers 8a and 8b. The coils 1 are positioned infboth zones, the flow ^being rst passed through the coils in zone 8a and then zone 8b, and then zone 8a, etc., as shown until the vapors exit. The furnace is heated by burner .|0I in combustion tunnel |0|a and the gases conduit lil. A portion of the thus preheated air is split by proper manipulation of dampers ||4 and H5, and passes through conduit IIB to provide combustion air for burner, |0|. vIn this trained catalyst be used, through lines and 20 vapors lare passed-through mist extractorand fractionator elements |2b and Jwashed with oil introduced through |2a to separate the heavy ends of the vapors. The vapors then pass through line i5 to the fractionator 33 in which the heavy oil is withdrawn through line 28 and vapors reiiuxed by reux produced ,by cooler 42. The polymer and reformed gasoline are-withdrawn into side stream receiver 30, and passed by pump"l|0 through the heater ,4| andintroduced into the stabilizer 46. The uncondensed vapors through line v43 are also introduced into stabilizer 40 by compressor 43a. In the stabilizer' the vapors are separated into a stabilized 8W line, withdrawn .through 5| and cooler 53. e bottoms' are heated by circulating through line 41, heater and line 50. Refluxis obtained by as a reflux. I dquidfraction withdrawn through the condensation of the vapors, withdrawn f through'by-pass 54, valve 55, condenser 54h and 'condensate' 'collected in 54",returned through 54a 75 fashion cold air," and if desired, blue gases recycled bythe circulation of the portion of combustion stream fromconduit |02; is circulated over the .coils in chamber 8. Chamber 8b is therefore maintained at considerably lower temperature from chamber 8a. Wall |'00 is preferably made of heat insulating material which isl suitable for high temperature operation such as qtire brick or diatomaceous earth vbricks. By proper circulation of air any desired difference in temperature may be maintained. It is understood thatinstead of passing the reaction material ilrst through the coils in chambers '8a, then through chamber 8b and then through chamber 8a, etc., the vapors may be p sed in anynuinber of passes through the coils n chamber 0a, and

then to chamber 8b to pass in' the chosen number of passes. Thus, the vapors may be passed to 'chamber 8a to carry on the reforming reaction, and then passed through chamber y8b for polymerization. The gases after exiting from chamber 8b are thengtreated as-shown in Figure 4.A -It-wi1l be understood that the furnace construction and flow shown in Figure 5 nay also be used in place of the .furnaces shown in Figures 1, 2 and 3. Y t

- in operating the reaction in Figure 5, the coils in chamber 8a shall be maintained from 930- 1020 F. while the coils in chamber 8b shall be 'at about G40-'120 F. Infthis case4 the catalyst tion in 4 and 5 are given with relation to catalyzed reactions. the process there described may also be carried out as an uncatalyred reaction b'y omitting the catalyst. In the case of Fig. 5 uncatalyzed operation, the temperature plane in zone 8a should be relatively higher in, the-range of 1000-1300 l". and the temperature in zone 8b should be lower inthe range of 750- 950 F. c

Figure 6 shows a modification wherein the reforming and polymerization reaction lis sepa'- rated, and the polymerized and reformed matef t rials are combined for treatment to producey a blended, stabilized, polymerized and reformed gasoline. Feed composed of petroleum fractions, for instance kerosene and gasoline, is introduced through line I, into fractionator 8l. A side cut cated.4 The temperature may be regulated independently ofcoil Il. Ihepressure in coil Il may be independently controlled vby regulating valve 90a. yThe temperature in coil 1 may, depending uponthecatalystbefmmoO-IOSOF. andthe ,pressuresfrom about'l50-500 lbs. 1f uncatalyzed.'

the ten'iperature may be between F.,

while in coil Il, the-pressuresmay be around 500-5000 lbs., and the from 230- '150' F., depending uponthe catalyst employed. Any of the polymerizing catalysts previously described may be employed. Mixed catalyst slurry 'is removed through chamber i2. This will dehaving an intermediate boiling range is with- 1 drawn through line ia by pump 2 and sent through heat exchange la into reforming chamber 1 positioned in furnace I. Reformed gasoline is then contacted with the dousing oil composed of fuel oil introduced through Il, where it is partially cooled and then passed through heat exchange coil tb. It meets in line l DOIYmerized material introduced through line Il. 'l'he mixture of polymeriud and reformed gasoline into separator I2 and through mist extractor lfb. -The heavyends are withdrawn through It and the uncondensedwapors of a temperature from 425-450' F. areremoved through line Il. then passedA into the stripper and fractionator Il where, by the aid of the feed i land the reboiler Ila and Vreflux coil 42 in fractionatingchamber Stb, it is fractionated into heavy ends 2l, recycle stock la and the side cut Jof reformed and polymerized gasoline withdrawn through line Ila. Redux is providedby coil I2. The uncondensed vapors are withdrawn through line ll. The side cut lila is passed by pump 40 into heater ll and into the stabilizer 4I. The uncondensed vapors are passed by pump 43a, line into the stabilizer 46; In this stabilizer the gasoline is stabilized by the aidof reboiler a and redux pro,- vided by the condensation of gases withdrawn through valve Il, line and lla and condenser Nb. Stabilized gasoline is withdrawn through Il, and liquefied gases cdntaining the butanes, propanes, butylenes, propylenes, ethane and ethylenes pass through line Ita into collecting chamber Il. for recycling by pump Il through line 2l into line Il. In this line it meetsadditional link materials through line Il. The oommingled gases are then passed into heat exchanger lia into polymerization coil Il positioned in furnace l2. The hot gases are doused by mixing with a dousing medium such as gas oil. fuel oil, or kerosens. or gasoline introduced through Il and through heat exchanger lib and through I. 'as previously described. l

The reaction in coil fl may be 'uncataly'sed or catalyzed. Ifcatalyzedthecatalystmaybeany one of the reforming catalysts hereinabove indipendonthecatalystsndstockchosenaswillbe vunderstood from what hasbeen said previously. If the reactions in coilll are uncatalysed, the l temperature may range' from 850-050 F.

The foregoing description of the several modifications yof my invention d above are not to be considered aslimitlng since many variationsmaybemadewithintheseopeofthefollowing claims by those skilled in the art without departing fromthe spirit thereof.A f

The present application is a division of my copending application, -Serial No. 35,702, "filed August l2, 1935. L

I claim:

l. A process for the combined reforming and vpolymerizsation of hydrocarbons which comversturen the neighborhood o:y 'mo-oso' r'. snsprises heatingtoaein'theneig'hborhood of '10o-930 Ea mixture of hydrocarbons within the gasolinennse and of four-andlesscarbonatomsinthepresenceofa' mixture of. different catalysts one of 'said catalysts being active to promote reforming of said hydrocarbonswithinthe'gasolinerangeatatemtheotherofsaidcatalysiabe'ingactivetopromote polymerization of said hydrocarbons of less than four carbon atoms at said temperature and separating a reformed and polymer gasoline from said heated mixture. A

2. A process of combined polymerization and y reforming which comprises heating to a temperature within the range of V-10601".4 and a prasure within therangeof751500lbs. amixtureof within the' gasoline-range and hydrocarbons y.of/four and ls carbon atoms t CERTIFICATE voF cbRREcTIoN.

PHILIP sUBKow.

It is hereby certified tht error appear in vthe print-.eq specification of the above numbered vpatent requiring correction as follosr Page l, second column, line 5-11., for "propane" read propone-; pag'e 7', first column, line 8, for "pressure" read -prese.nce; pge 9*,first column, line for "propane" read--propene--q page .10, first column, `1ine 52, for

"link" read -1ike'; and that thesaid LetterslPatvent -should be read with this .correction therein that the samemgy conform to 'therecr-d of 'thoA vcasse in the Patent Office. A l

'l Signed and sealed. this 21st day of vApril, A.. 'DQ 19ML Henry Van ,if'scla'lm v(Seal) I Acting Commissioner of Patents. 

